CN103804174B - A kind of organic acid process for purification - Google Patents

A kind of organic acid process for purification Download PDF

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CN103804174B
CN103804174B CN201210442788.2A CN201210442788A CN103804174B CN 103804174 B CN103804174 B CN 103804174B CN 201210442788 A CN201210442788 A CN 201210442788A CN 103804174 B CN103804174 B CN 103804174B
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CN103804174A (en
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高大成
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China Petroleum and Chemical Corp
Sinopec Fushun Research Institute of Petroleum and Petrochemicals
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China Petroleum and Chemical Corp
Sinopec Fushun Research Institute of Petroleum and Petrochemicals
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
    • C07C51/42—Separation; Purification; Stabilisation; Use of additives
    • C07C51/47—Separation; Purification; Stabilisation; Use of additives by solid-liquid treatment; by chemisorption
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
    • C07C51/42—Separation; Purification; Stabilisation; Use of additives
    • C07C51/43—Separation; Purification; Stabilisation; Use of additives by change of the physical state, e.g. crystallisation
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
    • C07C51/42—Separation; Purification; Stabilisation; Use of additives
    • C07C51/48—Separation; Purification; Stabilisation; Use of additives by liquid-liquid treatment

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  • Organic Chemistry (AREA)
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  • Oil, Petroleum & Natural Gas (AREA)
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  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

The invention discloses a kind of organic acid process for purification.The method comprises: I, will stop fermented liquid heat inactivation; II, acidifying make organic acid crystallization separate out, and obtain organic acid crystallization liquid; III, organic acid filter cake organic acid crystallization liquid or filtration obtained mixes with organic solvent that organic acid is dissolved, and wherein adds appropriate basic solution, then carries out organic phase and aqueous phase separation; Organic phase after IV, separation, after washing, adds sorbent material, filtering and removing solid substance; The organic phase that V, step IV obtain is cooled to organic acid crystallization and separates out, and after filtration, drying obtains the organic acid production refined.The inventive method with an organic solvent refines organic acid with basic solution, not only shortens technical process, saves the inputs such as equipment, time and energy consumption, and can obtain the polymerization-grade product that purity is high, total nitrogen content is low, be more suitable for suitability for industrialized production.

Description

A kind of organic acid process for purification
Technical field
The present invention relates to a kind of organic acid process for purification, from fermented liquid, particularly obtain high purity organic acid method.
Background technology
The organic acid molecule general formula of indication of the present invention is C nh 2n-2o 4, wherein n is 10-18, is that microorganism utilizes the fermentation such as liquid wax and the meta-bolites that obtains.Its fermented liquid is complicated heterogeneous system, secretory product etc. wherein containing unreacted carbon source, microorganism cells and fragment, the substratum do not utilized and meta-bolites and microorganism, especially wherein to grade impurity containing a large amount of protein, pigment and ash, have a strong impact on purity and the application of product, and bring difficulty to this kind organic acid Extractive technology.
At present, very high to this kind organic acid purity requirement on market, particularly the purity requirement of polymerization-grade is higher, general requirement organic acid list acid purity is at more than 98.5wt%, total nitrogen < 30 μ g/g, only has at present and could obtain with organic solvent method purification the polymerization-grade product meeting this and require, and generally, even if purity reaches requirement, its total nitrogen content is still more difficult reaches requirement.
In CN01142806.6, with long-chain biatomic acid dry powder for raw material, use acetone, methyl alcohol and ethanol as solvent refining long-chain biatomic acid.The diprotic acid of this method first in fermented liquid is first after charcoal absorption, then acidizing crystal, filtration, washing and dry diprotic acid crystalli-zation cake obtain long-chain biatomic acid dry powder, then adopts organic solvent to refine.The raw material that the method is refined is that moisture filter cake obtains diprotic acid dry powder after drying, raw aqueous quantitative limitation is reduced to the turndown ratio of the method, adds the equipment that thick acid is dry, causes this technical process longer, add production cost.And the method is in the aqueous solution obtaining the alkaline diprotic acid sodium salt before diprotic acid crystalli-zation cake and in solvent refining processes, carry out twice charcoal absorption process altogether, those skilled in the relevant art understand, increase an activated carbon treatment process, facility investment and production cost can be increased, and activated carbon dosage is directly proportional to the loss of product, and activated carbon dosage is larger, the yield of product is lower.And when organic solvent refines diprotic acid, adopt sorbent material generally can reach the requirement of decolouring, but still the more difficult small molecular protein removed wherein, make total nitrogen content undesirable.
In long-chain biatomic acid process for purification disclosed in CN200410018255.7, first pre-treatment is carried out to fermentation method reaction solution, to remove thalline wherein and residual alkane or lipid acid, obtain organic acid clear liquid, then carry out acidizing crystal, acidizing crystal liquid obtains organic acid crude product through filter press again; Finally the crude product obtained refined in high vacuum conditions by wiped film vaporization, short course distillation device or adopt organic solvent to refine.After the diprotic acid crude product that the method obtains and solvent are dissolved, filtration etc. is not taked to remove the operation steps of insoluble impurities, in decrease temperature crystalline process, insoluble impurities must adsorb crystal surface like this, have impact on product purity, brings bad impact to the application of product.And the solvent treatment diprotic acid process in the method, include the solvent recrystallization operation of twice, solvent consumption is larger, add the burden that solvent recuperation is refining, cause operating process comparatively complicated, and the diprotic acid purity adopting solvent method to refine to obtain is the highest only 98.75wt%, produce slightly fluctuate time, just may can not get qualified product.
Summary of the invention
For the deficiencies in the prior art, the invention provides a kind of organic acid process for purification.Compared with prior art, the inventive method technique is simple, and energy consumption is low, and supplies consumption is few, and the organic acid purity obtained is high, and the foreign matter content such as small protein and pigment is low, is more suitable for suitability for industrialized production.
Organic acid process for purification of the present invention, comprising:
I, fermented liquid heat inactivation will be stopped;
II, acidifying make organic acid crystallization separate out, and obtain organic acid crystallization liquid;
III, organic acid filter cake organic acid crystallization liquid or filtration obtained mixes with organic solvent that organic acid is dissolved, described organic solvent is one or more in ketone, ester class, alkane, naphthenic hydrocarbon, aromatic hydrocarbons, wherein in above-mentioned system, add the basic solution that mass concentration is 0.5% ~ 30.0%, be preferably 1.0wt% ~ 15.0wt%, the add-on of basic solution is the 20wt% ~ 500wt% of organic acid butt weight, be preferably 50wt% ~ 200wt%, after mixing, carry out organic phase and aqueous phase separation;
After organic phase washed with water after IV, separation, add sorbent material, filtering and removing solid substance;
The organic phase that V, step IV obtain is cooled to organic acid crystallization and separates out, and after filtration, drying obtains the organic acid production refined.
In the inventive method, stopping fermented liquid described in step I is that microorganism utilizes liquid wax to ferment the meta-bolites obtained, and the organic acid molecule general formula wherein contained is C nh 2n-2o 4, wherein n is 10-18, and organic acid can be single a kind of organic acid, also can be mixed organic acid.After stopping fermented liquid heat inactivation, can carry out the impurity such as filtering and removing thalline, filtration can adopt the ordinary methods such as membrane filtration and equipment.Also can in Step II I the impurity such as filtering and removing thalline.Heat inactivation temperature is generally 75 DEG C ~ 100 DEG C.
In the inventive method, the acidifying described in Step II can adopt ordinary method to carry out.The pH value of described acidifying is 2.0 ~ 4.0, and Heating temperature is 80 ~ 100 DEG C.The above-mentioned acidifying of the present invention acid used can be the H of any concentration 2sO 4, HNO 3, HCl or H 3pO 4.
Step II I organic solvent used is one or more in ketone, ester class, alkane, naphthenic hydrocarbon, aromatic hydrocarbons, preferably wherein be insoluble in water or water-fast organic solvent, be more preferably one or more in dipropyl ketone, isobutyl acetate, dodecane, ethylcyclohexane, toluene.
In the inventive method, the weight ratio of organic solvent and organic acid butt is 1:1 ~ 15:1, is preferably 2:1 ~ 7:1.Organic acid crystallization liquid or organic acid filter cake and organic solvent preferably dissolve in a heated condition, and Heating temperature is generally 80 DEG C ~ 150 DEG C, preferably 90 ~ 120 DEG C, concrete according to selecting the boiling point of solvent to determine, generally lower than the boiling temperature of used solvent.
Described basic solution is selected from one or more the solution in sodium bicarbonate, sodium carbonate, sodium hydroxide, saleratus, salt of wormwood, potassium hydroxide.
In the inventive method, can add in step IV deionized water wash organic phase once or once more than, and isolate aqueous phase.
In the inventive method, sorbent material in step IV is one or more in gac, atlapulgite etc., and be preferably gac, add-on is the 0.01wt% ~ 2.0wt% of organic acid butt weight, be preferably 0.01wt% ~ 1.0wt%, adsorption time is 30min ~ 60min.
In the inventive method, till in step V, crystallisation by cooling temperature is generally and makes organic acid sufficient crystallising, temperature is generally 10 DEG C ~ 30 DEG C.
In the inventive method, the organic solvent filtrate obtained in step V, can recycle.
The inventive method can obtain the organic acid production of highly purified single kind, also can obtain mixed organic acid product.
Although it is this area ordinary method that organic solvent method refines such organic acid, but the optimum solvent used in existing method and best operational path, also purity requires (98.5%) purity a little more than product quality indicator can only be obtained, this is disadvantageous to the stably manufactured of full scale plant, when production is slightly fluctuated, just qualified product may be can not get.The present inventor finds, appropriate alkaline aqueous solution is added to containing in organic acid organic phase, the organic acid in organic phase is made to be converted into water miscible organic acid salt, be uniformly mixed the lower impurity that can make in organic phase, as small protein and pigment etc., moved in aqueous phase mutually by organic solvent, and only use the sorbent material of minute quantity just can obtain purity be greater than 99.8% and total nitrogen be less than the organic acid production of 30 μ g/g.Do not add alkali lye as do not added in organic phase, although organic acid purity can reach the index of market demands, the protein content in product, also can the application of limits product higher than 30 μ g/g.In the art, it has been very difficult that object quality product reaches polymerization-grade index request, purity often improves 0.1 percentage point and total nitrogen to reduce by 1 μ g/g is all very difficult on this basis, and be also all significant and value, this is to the steady running of guarantee full scale plant, improve the aspects such as conforming product rate, having important effect, is also obviously to the quality influence of the polymerization products such as follow-up synthesizing engineering plastic.
The inventive method, while acquisition high purity organic acid production, the advantages such as also have technological process simple, energy consumption is low, and supplies consumption is few.
Embodiment
Process for purification of the present invention is further illustrated below by embodiment.In the present invention, wt% is massfraction.
In the inventive method, containing liquid wax, thalline, the substratum do not utilized, meta-bolites and microorganism secretion thing etc. in fermented liquid, especially wherein containing impurity such as a large amount of protein, pigments.Organic acid crystallization liquid can adopt this area usual method to obtain, as adopted following at least one scheme:
(1) will stop fermented liquid heat and leave standstill, and divide the liquid wax going to upper strata, then cooling also filtration sterilization, obtains filtrate and is acidified with acid to pH2.0 ~ 4.0, and heat simultaneously, obtain organic acid crystallization liquid, or aqueous solutions of organic acids filtration is obtained filter cake;
Actual conditions is: termination fermented liquid is heated 75 DEG C ~ 100 DEG C, adjust ph >=9, leave standstill, then divide the liquid wax that upper strata is residual, then be cooled to 60 DEG C ~ 80 DEG C, through micro-filtration and or ultrafiltration apparatus, cross impurity such as filtering thalline and obtain clear liquid, the clear liquid obtained is added acid for adjusting pH value to 2.0 ~ 4.0, and be heated to 80 DEG C ~ 100 DEG C, obtain organic acid crystallization liquid, or aqueous solutions of organic acids filtration is obtained filter cake.
(2) fermented liquid is heated to 75 DEG C ~ 100 DEG C, and is acidified to pH value 2.0 ~ 4.0, leave standstill, Separation and Recovery liquid wax, obtains organic acid crystallization liquid, or aqueous solutions of organic acids filtration is obtained filter cake.
(3) fermented liquid is heated to 75 DEG C ~ 90 DEG C, enters micro-filtration or ultra-filtration equipment, remove thalline and liquid wax etc., the acidification of filtrate obtained to pH value 2.0 ~ 4.0, and is heated to 80 DEG C ~ 100 DEG C, obtains organic acid crystallization liquid, or aqueous solutions of organic acids filtration is obtained filter cake.
Embodiment 1
Get 200ml and obtain C by Candida tropicalis fermentation 12h 22o 4organic acid fermentation liquid, concentration is the fermented liquid of 160g/l.Be heated to 80 DEG C, use H 2sO 4pH value is adjusted to 3.0, leaves standstill 2h, point liquid wax going solution residual, obtains the C of mycetome 12h 22o 4organic acid crystallization liquid.
The C obtaining mycetome 12h 22o 4organic acid crystallization liquid and dipropyl ketone (dipropyl ketone and C 12h 22o 4weight ratio is 6:1) after mixing, add 1.0wt%NaOH aqueous solution 32g, and be heated to 115 DEG C, static 60min, point sub-cloud aqueous phase; In solvent phase, add 30ml deionized water wash organic phase again, again divide phase of anhydrating; Subsequently to adding 0.2g gac insulation decolouring 30min in organic phase, then cross and filter gac, the organic phase after decolouring is cooled to 19 DEG C of crystallizations and obtains C 12h 22o 4organic acid, then obtain product through drying step.Quality product is in table 1.
Embodiment 2
Get 200ml and obtain C by Candida tropicalis fermentation 12h 22o 4organic acid fermentation liquid, concentration is the fermented liquid of 160g/l, regulate pH to 10.0, be heated to 80 DEG C, leave standstill 2h, divide the liquid wax going solution residual, lower floor's solution microfiltration equipment, filtering the impurity such as thalline obtains clear liquid excessively, and the clear liquid obtained is added acid for adjusting pH value to 3.5, and be heated to 80 DEG C, obtain organic acid crystallization liquid.
The C obtaining mycetome 12h 22o 4organic acid crystallization liquid and isobutyl acetate (isobutyl acetate and C 12h 22o 4weight ratio is 4:1) mixing, add 10wt%KOH aqueous solution 20g to mixed solution, mix and be heated to 135 DEG C, static 60min, point sub-cloud aqueous phase; In solvent phase, add 50ml deionized water wash organic phase again, again divide phase of anhydrating; In organic phase, add 0.16g gac insulation decolouring 30min, then cross and filter gac, the organic phase after decolouring is cooled to 28 DEG C of crystallizations and obtains C 12h 22o 4organic acid, then obtain product through drying step.Quality product is in table 1.
Embodiment 3
Get 200ml and obtain C by Candida tropicalis fermentation 13h 24o 4organic acid fermentation liquid, concentration is the fermented liquid of 154g/l.Be heated to 70 DEG C, through ceramic micro filter membrane filtration, the liquid wax removing thalline and remnants obtains filtrate.H is added in filtrate 2sO 4adjust ph to 2.4, and be heated to 95 DEG C, obtain C 13h 24o 4organic acid crystallization liquid, is cooled to room temperature filtration and obtains organic acid filter cake.
The C obtained 13h 24o 4organic acid filter cake and dodecane (dodecane and C 13h 24o 4weight ratio is 8:1) mixing, add 15wt%Na wherein 2cO 3aqueous solution 40g, mixes and is heated to 120 DEG C, static 60min, point sub-cloud aqueous phase; In solvent phase, add 60ml deionized water wash organic phase again, again divide phase of anhydrating; Add 0.3g gac insulation decolouring 30min to organic phase, then cross and filter gac, the organic phase after decolouring is cooled to 16 DEG C of crystallizations and obtains C 13h 24o 4organic acid, then obtain product through drying step.Quality product is in table 1.
Embodiment 4
Get the C that 200ml concentration is 145g/l 14h 26o 4organic acid fermentation liquid, is heated to 70 DEG C, and through ceramic micro filter membrane filtration, the liquid wax removing thalline and remnants obtains filtrate.H is added in filtrate 2sO 4adjust ph to 3.0, and be heated to 95 DEG C, obtain C 14h 26o 4organic acid crystallization liquid.
The C obtained 14h 26o 4organic acid crystallization liquid and ethylcyclohexane (ethylcyclohexane and C 14h 26o 4weight ratio is 6:1) mixing, add 7wt%NaHCO wherein 3aqueous solution 58g, mixes and is heated to 95 DEG C, static 60min, point sub-cloud aqueous phase; In solvent phase, add 30ml deionized water wash organic phase again, again divide phase of anhydrating; In organic phase, add 0.15g gac insulation decolouring 30min, then cross and filter gac, the organic phase after decolouring is cooled to 22 DEG C of crystallizations and obtains C 14h 26o 4organic acid, then obtain product through drying step.Quality product is in table 1.
Embodiment 5
Get the C that 200ml concentration is 135g/l 13h 24o 4and C 14h 26o 4organic acid fermentation liquid, is heated to 70 DEG C, and through ceramic micro filter membrane filtration, the liquid wax removing thalline and remnants obtains filtrate.H is added in filtrate 2sO 4adjust ph to 2.4, and be heated to 95 DEG C, obtain mixed C 13h 24o 4and C 14h 26o 4organic acid crystallization liquid.
The C obtained 13h 24o 4and C 14h 26o 4organic acid crystallization liquid and toluene (toluene and C 13h 24o 4and C 14h 26o 4weight ratio is 7:1) be mixed and heated to 95 DEG C, until completely dissolved, static 60min, point sub-cloud aqueous phase; 10wt%K is added in organic phase 2cO 3aqueous solution 40g, mixes and is heated to 140 DEG C, static 60min, point sub-cloud aqueous phase; In solvent phase, add 80ml deionized water wash organic phase again, again divide phase of anhydrating; In organic phase, add 0.35g gac insulation decolouring 30min, then cross and filter gac, the organic phase after decolouring is cooled to 15 DEG C of crystallizations and obtains mixed C 13h 24o 4and C 14h 26o 4organic acid, then obtain product through drying step.Quality product is in table 1.
Comparative example 1
Get 200ml and obtain C by Candida tropicalis fermentation 12h 22o 4organic acid fermentation liquid, concentration is the fermented liquid of 160g/l.Be heated to 80 DEG C, use H 2sO 4pH value is adjusted to 3.0, leaves standstill 2h, point liquid wax going solution residual, obtains the C of mycetome 12h 22o 4organic acid crystallization liquid.
The C obtaining mycetome 12h 22o 4organic acid crystallization liquid and dipropyl ketone (dipropyl ketone and C 12h 22o 4weight ratio is 6:1) after mixing, static 60min, point sub-cloud aqueous phase; In solvent phase, add 30ml deionized water wash organic phase again, again divide phase of anhydrating; Subsequently to adding 0.2g gac insulation decolouring 30min in organic phase, then cross and filter gac, the organic phase after decolouring is cooled to 19 DEG C of crystallizations and obtains C 12h 22o 4organic acid, then obtain product through drying step.Quality product is in table 1.
Table 1 organic acid production quality
Project Acid content, wt% Total nitrogen, μ g/g
Example 1 99.86 ＜30
Example 2 99.89 ＜30
Example 3 99.95 ＜30
Example 4 99.97 ＜30
Example 5 99.94 ＜30
Comparative example 1 99.35 81

Claims (12)

1. an organic acid process for purification, comprising:
I, fermented liquid heat inactivation will be stopped;
II, acidifying make organic acid crystallization separate out, and obtain organic acid crystallization liquid;
III, organic acid filter cake organic acid crystallization liquid or filtration obtained mixes with organic solvent that organic acid is dissolved, wherein in above-mentioned system, add the basic solution that mass concentration is 0.5% ~ 30.0%, the add-on of basic solution is the 20wt% ~ 500wt% of organic acid butt weight, carries out organic phase and aqueous phase separation after mixing;
After organic phase washed with water after IV, separation, add sorbent material, filtering and removing solid substance;
The organic phase that V, step IV obtain is cooled to organic acid crystallization and separates out, and after filtration, drying obtains the organic acid production refined;
Described organic solvent is one or more in dipropyl ketone, isobutyl acetate, dodecane, ethylcyclohexane, toluene, described basic solution is selected from one or more the solution in sodium bicarbonate, sodium carbonate, sodium hydroxide, saleratus, salt of wormwood, potassium hydroxide, and described organic acid molecule general formula is C nh 2n-2o 4, wherein n is 10-18, and organic acid is single a kind of organic acid or is mixed organic acid.
2. in accordance with the method for claim 1, it is characterized in that the mass concentration of described basic solution is 1.0wt% ~ 15.0wt%.
3. in accordance with the method for claim 1, it is characterized in that the add-on of described basic solution is the 50wt% ~ 200wt% of organic acid butt weight.
4. in accordance with the method for claim 1, it is characterized in that step I heat inactivation temperature is 75 DEG C ~ 100 DEG C.
5. in accordance with the method for claim 1, it is characterized in that the pH value of acidifying described in Step II is 2.0 ~ 4.0, Heating temperature is 80 ~ 100 DEG C, and acidifying acid used is the H of any concentration 2sO 4, HNO 3, HCl or H 3pO 4.
6. in accordance with the method for claim 1, it is characterized in that in Step II I, the weight ratio of organic solvent and organic acid butt is 1:1 ~ 15:1.
7. in accordance with the method for claim 1, it is characterized in that in Step II I, the weight ratio of organic solvent and organic acid butt is 2:1 ~ 7:1.
8. in accordance with the method for claim 1, it is characterized in that in Step II I, organic acid crystallization liquid or organic acid filter cake and organic solvent dissolve in a heated condition, and Heating temperature is 80 DEG C ~ 150 DEG C.
9. in accordance with the method for claim 1, the sorbent material that it is characterized in that in step IV is one or more in gac, atlapulgite, and add-on is the 0.01wt% ~ 2.0wt% of organic acid butt weight, and adsorption time is 30min ~ 60min.
10. the sorbent material add-on that in accordance with the method for claim 1, it is characterized in that in step IV is the 0.01wt% ~ 1.0wt% of organic acid butt weight.
11. in accordance with the method for claim 1, it is characterized in that in Step II, and organic acid crystallization liquid adopts following at least one scheme:
(1) termination fermented liquid be heated to 75 DEG C ~ 100 DEG C and leave standstill, dividing the liquid wax going to upper strata, then cooling also filtration sterilization, obtains filtrate and is acidified with acid to pH2.0 ~ 4.0, and be heated to 80 DEG C ~ 100 DEG C simultaneously, obtain organic acid crystallization liquid;
(2) termination fermented liquid is heated to 75 DEG C ~ 100 DEG C, and is acidified to pH value 2.0 ~ 4.0, leave standstill, Separation and Recovery liquid wax, obtains organic acid crystallization liquid;
(3) fermented liquid is heated to 75 DEG C ~ 90 DEG C, enters micro-filtration or ultra-filtration equipment, remove thalline and liquid wax, the acidification of filtrate obtained to pH value 2.0 ~ 4.0, and is heated to 80 DEG C ~ 100 DEG C, obtains organic acid crystallization liquid.
12. in accordance with the method for claim 1, it is characterized in that in step V, crystallisation by cooling temperature is 10 DEG C ~ 30 DEG C.
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CN103965035B (en) * 2013-01-30 2016-01-27 上海凯赛生物技术研发中心有限公司 The process for purification of long-chain biatomic acid
CN106673994A (en) * 2015-11-09 2017-05-17 中国石油化工股份有限公司 Refining method for long-chain organic acid
CN106478410A (en) * 2015-11-25 2017-03-08 衡阳屹顺化工有限公司 A kind of preparation method of organic acid
CN115232000A (en) * 2021-04-25 2022-10-25 中国石油化工股份有限公司 Method for refining pyromellitic formic acid

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CN1255483A (en) * 1998-12-03 2000-06-07 中国石油化工集团公司 Process for refining long-chain biatomic acid
CN1289757A (en) * 1999-09-29 2001-04-04 中国石油化工集团公司 Process for extracting alpha-or omege-alkadicarboxylic acid from fermented liquid and refining it

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JPS5886090A (en) * 1981-11-17 1983-05-23 Mitsui Petrochem Ind Ltd Separation of dicarboxylic acid

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CN1255483A (en) * 1998-12-03 2000-06-07 中国石油化工集团公司 Process for refining long-chain biatomic acid
CN1289757A (en) * 1999-09-29 2001-04-04 中国石油化工集团公司 Process for extracting alpha-or omege-alkadicarboxylic acid from fermented liquid and refining it

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